Process for the manufacture of boric acid from sodium borate



l P. J. o'BRn-:N ETAL 2,545,746 PRocEss FOR THE MANUFACTURE oF Bomc ACID FROM soDIUM BoRATE Filed oct. 29, 194e March 20, 1951 15a z-cls-Jass .Z7 D E1-55.27 J-T-Z 5.175.752 Va :Za Sheff-JE' Patented Mar. 20, 1951 PROCESS FOR THE MANUFACTURE F BOB/IC ACID FROM SODIUM BOR/ATE Patrick Joseph OBrien and Ronald Valda Chettle,

Long Beach, Calif., assignors, by mesne assignments, to Borax Consolidated, Limited, London, England, a corporation of Great Britain and Northern Ireland Application October 29, 1946, Serial No. 706,336

This invention relates to the production of boric acid and sodium sulfate from natural barata-containing ores andthe like. We make use of the inverse temperature relations of the respective solubilities of borc acid and sodium sulfate in aqueous solution, by which sulfate can be precipitated out from a suitably acidulated mother liquor at a relatively elevated temperaing approximately to boiling point, addition of sunicient sulfuric acid to convert the added sodium to sulfate, removal of the precipitated sodium sulfate from the solution, cooling of the solution to a suitable temperature, such as 110 at which boric acid crystallizes out. After removal of the boric acid by centrifuging or the like, the mother liquor'is recirculated and the cycle is repeated.

Such a process is relatively straightforward vwhen artificial or already processed alkali borates are used as raw materials, .but if sodium borate in the form of naturally occurring ores is to be used the process is complicated lby the necessity of dissolvinglthe salts from the ore in the mother liquor and then separating out and discarding the insoluble material. The coarser fraction of rthe insolubles can be removed without undue loss of the salt content of the solution by means of a conventional classier; and nearly the Whole of the remaining relatively iine insolubles can then Ibe removed from the main bulk of the solution 'by means of a conventional thickener or settling tank. However, the underflow from this thick- 'ener must include enough of the solution to carry oli the sludge, and this solution contains a significant fraction of the original salts. This might be returned to the system by ltering the underflow solution',v but this would be relatively expensive both in equipment and in operating charges.

Itis usual under such'ccnditions to use two lth'iclzeners in series, the underflow from the rst 'being introduced into the secondof the series alongwith a quantity of additional solvent to act as a wash and dilute the solution. Part of the Ydiluted solution in the second thiokener is used to carry out the sludge, forming what we call the second underflow; and part forms the second overflow, which can be re-introduced into the system and its contained` solutes thus saved. This 'procedure can ne continued, adding successive 1 Claim. (Cl. 23-149) tively expensive means.

thickening units to the series, until the underflow from the last unit is sufficiently dilute that the loss of solutes isnot serious, or until the overow from a further unit would be so dilute that it could not successfully be re-introduced into the system.

In the present instance, as will be shown in detail below, the overflow fromfthe second thickenerA of such a series is lalready too dilute to be combined with the overflowfrom the rst thickener'and successfully treated in combination with it. This is because thev combined solution after acidulation wouldcontain so low a concentration ofzsodium sulfate that less than the required amount of thissubstance would vprecipitate out. Therefore, it would appear necessary that the entire salt content of the underflow from the first thickener be either wasted or recovered by rela- 'Howeven Wevhaveifound that a second thickener can eflicientli be introduced in series after the first, the overflow from the second thickener being separately treated in a secondary circuit and re-introducel into the main system at a later stage after the precipitation of sodium sulfate from the'primary circuit has already lbeen accomplished. When this is done according to our invention'it is possible to recover substantially the Whole of both the boric acid and the sodium sulfate containedv in the secondary circuit, that is, in the second' overflow, Vand to accomplish this with relatively little additional equipment or operating expense. 1

When the borate used as raw material for such a process is borax` (Na2B4Of1-10H2O), containing ten-mols of water per mol of sodium tetraborate, there is anct gain of five mols of water from the chemical reactions. Also, it is convenient, if not necessary, infall such processes to add water at various stages of the cycle, for example as a washing agent inthe classifier and in the centrifuges; and in the' particular process which we have developed water is also added to the second thickener. Some water is removed from the system with the'wasted material, but in general, whether' the process is intendedto use straight boraX or boraX-containing oreY as a raw material, the water content-of the circulated liquor'tends to increase. An important object of our inventionis to eliminate sufcient water from the system to overcome and even to reverse this tendency, and to do this economically and without loss of salts. `This is accomplished during'the necessary cooling of the solution between precipitation of sodium sulfate and crystallization of movingthe sedimentat :26.

2,5 3 boric acid. By making use of the evaporation of water from the solution to produce the required cooling, we are able to lower the temperature and the water content of the solution by a single operation.

It is particularlypadvantageousin Acarrying out the above described procedure that'the solution in thesecondary circuit to combined with that of the primary circuit before the latter is concentrated and cooled by evaporationlto'crystallize out boric acid from it. Thep'rimary :solution by itself would containr-a .high .enough-con centration of sodium sulfateto..cause..someipre cipitation of sulfate even atfthelowered temperature, contaminating the boric acidfcrystals. Addition of the relatively dilute secondary solution to the primary solution before. tor duringhcooling tends to counteract the loss of "water" by evaporation. This maintains the concentration of the solution at a suciently low level to hold thesulfateinz=solution,andfyet .allows borictacid to crystallizefout-.to the required extent.

.--A clear understanding of-our 'inventionj and-of f further ,objects and --advantages YAthereof `will lbe obtained from the .following kdescription A, of an illustrative preferred embodiment, which.is.n0t,

,- however, intended to limitin anyway nthe scope of the invention.

.The-attached.drawingsFig. 1, is Aadizugramillustrating -schematically the main features 0f0301fromthe `solution infany suitable-'way, forex- -zour process: aS applied.v .ina ,oparticular r instance,

-and is a part of. this description.

zOurprocess is fa vcyc'flic-"one,ztheimother liquor being usedf overragai'n li-n-.thet processing :of successive: batches tof raw material. Although it ,-is assumed for purposes ofthe; present description e that y.the process is carried through in batches c of lim-itedsizerathertthan, as. yaa'continuous...flow process, it will be clear thatfa continuous .flow mayo also be .usedtin partr .all of.thevsystem, vap =propriate modifications `being.'madein theequip- .mei-1t.

In Fig-.1 we indicate at imahopper frommwhich ore` is adm-ittedsas desired into the dissolving tank l2, rfmother liquor being admitted through .the .l

,.pipe- I 3ffroma:storagei tank I4. Means forcontrolling f the rmotionl of :materials are :general-ly omittedv throughout the cfdiagra-m, sas; are= various otherfeatures ofK .t-herequipmentfwhichnare Jwell :understood mtthef-art. stirring uneans--withi-n` l the dissolver l2 are indicatedfat I6: for hastening .the fsolution: of thel'solublefraction: of -the sore, and steam coils Il are preferably;provided to raise the f `ten/iperature to :the :neighborhood of :130 for thesamefpurpose.

Thel mixturei ofthe resultingsolutionand. t-he l insoluble f fraction of` the .-oreais passed 1 through 1 some suitablemechanisrn indicatedf-fasvclassiner `,-20 to which,washcwatersmay1befadded1atf2Uaand in which .the larger'fsolids;.nisually,*approximating half :of the rtotal solidsyare. removed at:2 I' together '.witha `negligible part offthe solution. :The Amain bulkrof thesolution, :carrying inf suspensionl the remainder. of the insolublefmaterial; is carriedon -to the iirstthickener f25, -whichnis'typical-lyza .settling tank with conventional means for re- Enough solution, sand. preferablyI just: enough, is-ltaken, 01T v-at: 26- to .,fiuidizewand carrythisssediment, thefsediment and.solution l together rcomprising Avwhat we. call f vthe -rst under-flow. Thegreaterfpartof the solu- -itionfin the` rsttthickener leaveszthe tank at-Z'l, .constituting the rst over-flowyand carrying lonly af smallamount of 1very; iine 'solid 'materiaL -The Dlatter is removed in anysuitable-fway, suchras.-by

the primary filter press indicated at 30. The solution leaving this filter press at 3| is suitable for the extraction of sodium sulfate and then boric acid in the usual way. The entire proc- 5 .essingof thisY solution comprises-whatwe call the T'primary circuit of the system.

The solution from the primary iilter press is `taken to the sulfate reactor 50 where it is heated by suitable means, such as the steam coils indil'O :.cated' at15lgto1-'approximately 2105 F. An appropriate quantity of sulfuric acid is added to the solutionat 53 from the storage tank 55 to convert all NazO-in thesolution to sodium sulfate. This *.raiseslthe sulfatewconcentration above the solu- @;bi-litysat thisztemperature and causes the precipitation "of vanhydrous sodium sulfate. The amount ofsultate precipitated can be calculated from known solubility data and can be controlled byss'iitable control of the sodium sulfate concentration of the original mother liquor and of otherrelated factors. Since the process isto be .fcyclic, the quantityv of sodium sulfate toibe prefci-pitated must correspondto the total-quantity of sodium ,dissolvedafrom the original ore, less -thatcarriedaway at variousstages of thefprocf'ess asv/aste. As 'will become clear-later`the esodium-sulfate lprecipitated inY reactor 56 does not .necessarily correspond totheacid added at53.

Thegprecipitated sodium sulfate isremoved ample by centrifugingas illustrated; schematilcallyfat 6U, asmall amountof .wash water-being generally added. tothe-centrifuge as'at 60a. The precipitate is `dried :fand otherwise f processed as 1135 fmay 'be desired at 6l Vandiemerges-at 62 as a liinished product. AThe remaining solution lleaves ,centrifuge 'at 65 and istcarriedto the cooling :tank;1.!,"-wherethe'ltemperature is reduced (see 'fbelowl'causingboric-acid tocrystallize out. The "boric `acidcrystals-are removed from thesoluitionfas by centrifuge=15,the resulting solution "being returned at 'i8 to tank i4 as motherY liquor of the initial composition and suitable for repetition'of the.cycle.

We prefer' for practical reasons/todissolve the ore `initially ata temperaturenot much.above 130 F. The. combination. of.. mother liquor. and `dissolved' borates .thenpreferably conta-ins AB203 .anclLNazO in a, molar, ratio of.approximatelyA 3.2 to .1.l, .since this Y gives optimum solubility. for.the -.solubles ore.V fraction. It is thenl foundrin vpractice .that evenV if v thesmallest practicable amount iof vmothertliquoris .used for,each..unit` off ore,y the v -concentration oNazSOi in Athe. acidulatedsolution 'in sulfate reactor 5!! is .'onlyslightly higher than. is rnecessary in order toy precipitate .out the required amount. -ofv sodium sulfate. Therefore, Hanyprocedure which leads toappreciable further dilution of the..solutionsatl-this stage wouldfibe .,impracticable.

-Returning now vto the -iirst thickener underflow at-'26, its fluid component contains dissolved-salts in substantially thesameconcentration as those in the rst overflow at 3 I. However,.the solution -in theunderiiow` cannot beitreated for-precipita- -.tionrecoveryof the desired salts: because of the -'presence VVof insoluble material. If this entire lunderflow is rejected the dissolved salts z lost 7.0 amounttoen-appreciable fraction-'of the total salts contained inthe originalnore. It is there- *fore desirable to process this rst underiiow inra second thickener, indicated at 40, additional lwash iwater-being added asindicated at-4I lto dilute the solution, The-amount offdilute'dsolution: which must be removed with the Vsecond underow at 42 in order to carry off the sediment is approximately the same in volume as the 'undiluted solution in the first underflow. However,

" due to the dilution, a smaller quantity of salts is carried oil in the second underflow, the remainder of the salts passing from the second thickener at 43 as a practically clear solution which we call the second overflow. This is preferably passed through a filter press as indicated at 45, yielding a clear solution at 46.

Although a large fraction of the salts in the rst underflow have thus been saved by separation from the sediment, the second overflow is not suitable for treatment for recovery of these salts by the usual precipitation process (such as is carried on in reactor 50) since the salts to be removed are present in too low a concentration. `Even at the highest practicable temperature and after conversion of all the sodium to sulfate by acidulation, sodium sulfate will not precipitate out. Moreover, even if the filtered second overflow were to be combined at this stage with the first overflow, and the combined solution were to be passed through reactor 50 with the filtered first overflow, the concentration of sodium sulfate in the acidulated combined solution would be insuihcient to give the required amount of precipitation.

The answer which we have found for the above described problem is to treat the second overflow by a secondary circuit which by-passes the step of sulfate precipitation. From 4E the filtered solution is heated in tank 41 to approximately 180 F., and is then taken to the cooling tank 'l0 where it is combined with the solution coming from reactor 5D and centrifuge 6G in the primary circuit at a temperature somewhat below 210o F. Additional sulfuric acid is introduced into the secondary circuit at any convenient point, either directly into cooling tank 10, or preferably ahead of the cooling tank, for instance into tank 41 via the connection 'I I, in appropriate quantity to convert all of the sodium borate of the secondary circuit to sodium sulfate and boric acid. This sulfate remains in solution in the mother liquor through the remainder of the cycle. YHowever, this does not cumulatively increase the sodium sulfate concentration of the mother liquor, since the amount of sulfate removed from the primary circuit on each cycle corresponds to the total sodium introduced into the solution from the ore (less waste, as already described). Expressed in other terms, the amount of sulfate removed from the primary circuit takes care of the sulfate formed in both circuits. f

The combined solution in the cooling tank Ill may be considered to contain substantially only HsBOs and NazSOa, both these substances being in concentrations which are soluble at the initial temperature of about 180 F. As the temperature is reduced, the solution becomes supersaturated with respect to boric acid but not with respect to sodium sulfate, and crystals of substantially pure boric acid are formed. These are separated from the remaining solution in any suitable way, for example by means of a centrifuge as indicated at l5, wash water being ordinarily added as at a. The boric acid crystals are dried and otherwise processed at 16-as may be required, and emerge as a product of the system at l1. Theremaining solution leaves the centrifuge 15 at 18 and is returned to storage as mother liquor to carry out another cycle.

6. I 'The amount of boric acid thus thrown out of solution at 'I0 can be controlled by suitably controlling the concentration and temperature of the solution, provided, of course, that the sulfate' concentration is maintained enough lower than its solubility to prevent appreciable precipitation and resulting contamination of the boric acid produced. To maintain the system in balanced operation, the amount of boron removed from the solution as boric acid at 1li Should equal that added to the solution at I2 with the soluble ore fraction, less whatever is taken out of the system as waste.

Y The method which we preferably use for cooling the solution at 'lll is the evaporation of a part of the water content of the solution. This can be accomplished by blowing a current of relatively dry air over the iiuid surface in the tank, as indicated schematically at 12. Although a single cooling tank 'Ill is indicated in the figure, it will be understood that a battery of tanks can' beused, or that any other means can be used by which the solution is cooled either wholly or partly by evaporating part of its water content.

An important advantage of this method of cooling the solution-is that in addition to accomplishing the cooling function it reduces the water content of the solution. The exact amount of water which needs to be removed to bring the lsystem into balance depends on `many details of the process which will vary from one installation to another. When boraX is used as the raw material, whether in the form of ore or otherwise, 10 mols of crystallization water are introduced into the solution'with each mol of NazBiOv, and one additional mol of water is formed in the reaction with sulfuric acid. Six

of these eleven mols of water are removed in the four mols of boric acid formed, and the remaining ve must be removed from the solution in some other way. In addition to the net gain of water from the chemical reactions, the water balance is affected by other factors. These include the addition of water as such to the system, as wash water and the like, and the removal of water from the system in the solution which is rejected at various stages as waste.

In most systems these other factors are subject lto adjustmentwithin a limited range to Agive either a net gain of water or a small net loss. But a large, or even an appreciable, net loss of water due to these factors ordinarily results in impaired eiiciency of the system, and cannot in practice be made to overcome the water increase from the chemical reactions. However, in our process the water removed by evaporative cooling is suicient not only to balance the net increase of H2O from the chemical reactions but also to balance a considerable net increase due to the other factors mentioned. It is advantageous to have such a margin available,since the balance can then alwaysbe restored readily by adding water at some convenyient point in the cycle.

When the sodium sulfate, the boric acid, and the water are separately balanced for the system as a whole, as described above, the remaining mother solution which is returned from centrifuge 'l5 to tank I4 has the same composition as the original mother liquor that was taken from tank I4 to dissolver I2 at the start of the operation. The process can therefore be repeated indefinitely, either continuously oras a batch process. 1

It may be` pointed out that the'secondary circuit need not rejoin the primary circuit at the air cooler, but'can, at least in theory, rejoin it at any other point after sulfate reactor 50, and either before or after'cooling tank 10. For example, the solution leaving secondary lter 45 at 46 can be taken directly to mother liquor storage tank I4, the sulfuric acid needed to convert the Naz() in the secondary circuit solution to Na2S04' being added at any suitable point. The secondary circuit would then by-pass the step of boric acid crystallization as well as the step of sulfate precipitation. However, the total amount of boric acid crystallized out at would remain unchanged, this quantity being determined, as described above, to preserve the over-all balance of the system with respect to boric acid. v

In practice, we have found it advantageous to add the secondary solution to the primary solution before completion of the step of cooling'and concentration by air evaporation. The primary solution leaving sulfate reactor 50 is approximately saturatedwith Na2SO4. As the solution isv cooled by evaporation in cooling tank 10 the solubility of sulfate increases with decreasing temperature, but the concentration of the sulfate also increases, because of the removal of water fromthe solution.` These two factors may nearly balance, so-that if the primary solution is treated by itself in the cooling tank it remains virtually saturated with sulfate. Therefore some sulfate may be precipitated during the cooling operation, contaminating the boric acid crystals which are being formed at the same time. However, if the more dilute secondary solution is combined with the primary solution the latter is diluted, and this more dilute combined solution can then be cooled by evaporation and boric acid crystallized fromit without precipitation of sulfate. By heating the secondary solution as indicated at 4T, to approximately the temperature of the secondary solution before the two are combined, uneven precipitation is avoided.

We shall now give a rather detailed description of a typical manner in which our invention can be carried out in accordance with Fig. l. The figures used in this description arethe result of experience with a particular successful application of the invention, but are used here only by way of illustration and not as a limitation. For clarity of description certain small corrections, not essential to an understanding of our invention, are omitted in this description. Accordingly the figures given are necessarily somewhat approximate.

It is assumed that the ore toA be treated contains 31.5% insoluble material, the remainder being borax (Na2B40'r10H20), so that the B202 content is We use mother liquor with an initial composition of 8.1% HsBOs, 30.6% Na2S04, and 61.3% H2O. Under these conditions, in order to give a borate solution containing B203 and Na20 in the molar ratio of 3.2 to 1.0, it is necessary to use 330 lbs. of mother liquor per 100 lbs. of ore treated. The resulting solution then contains 10.0% B203, 2.8% Na20, 25.4% Na2S04, and 61.8% H2O, and carries with it about 8 lbs. of insoluble material per 100 lbs. of solution. Approximately half of the insolubles, comprising the Further separation occurs in firstthickener 25, approximately 16% of the solution being taken off in the underflow at 26 as a carrier for the remaining insolubles; and 84% of the solution comprising the first overflow, which is then filtered at 30, carried to sulfate reactor 50, and heated to 210 F. The composition of this solution is substantially that given above, and it therefore requires about 4.5 lbs. of 98% H2804 per '100 lbs. of solution to transform its contained sodium borate to sodium sulfate and boric acid. The acidulated solution has the composition 17.1% H2B03, 30.4% Na2S04, and 52.5% H20, or approximately 57.8 lbs. of Na2S04 per 100 lbs. of H20.

According to solubility data, at a temperature of 210 F. and in the presence of 17% H3B03, approximately 48.8 lbs. of Na2S04 can be dissolved per 100 lbs. of H2O. Therefore 9 lbs. of Na2S04 will be precipitated per 100 lbs. of H20, or about 4.7 lbs. per 100 lbs. of solution. However, to maintain an overall balance with respect to Na2S04, we preferably add about 0.65 1b. water per 100 lbs. of solution in sulfate reactor 50, thus reducing the amount of Na2S04 precipitated from that given above to about 4.4 lbs. After centrifugingat 60, the remaining solution, with the composition 17.9% H3B03, 27.0% Na2SO4, and 55.1% H20, goes to the cooling tank 10.

Returning now to the underiiow from rst thickener 25, comprising about 4 lbs. of insolubles and 16 lbs. of solution for each 100 lbs. of initial borate solution, this is taken to second thickener 40 and diluted by addition of 9.7 lbs. of water (calculated on the same basis). The resulting relatively dilute solution is divided into two approximately equal parts, one part carrying off the insolubles in the second underliow at 42, which is rejected, and the other, comprising the second overflow, forming the second circuit of the system. Acidulation of the second overflow requires about 2.7 lbs. of 98% H2804 per 100 lbs. of solution and results in a solution with the following composition: 10.7% H3B03, 19.1% Na2SO4, and 70.1% H20. This is combined with the solution from the primary circuit, from which a definite amount of Na2S04 has already been'removed, and the combined solution is cooled in cooling tank 10.

It may be pointed out here that the acidulated secondary solution contains less than 28 lbs. Na2S04 per '100 lbs. of water, compared with a solubility of over 45 lbs., so that no sulfate will precipitate out. Also, if this secondary solution were to be combined with the solution in the primary circuit before extraction of sulfate from the latter, the combined solution would contain only 52.7 lbs. Na2S04 per 100 lbs. of water, and would precipitate out an insuliicient quantity of sulfate (see above).

The combined solution actually produced in cooling tank 10 has an approximate composition of 16.9% H3B03, 25.8% Na2S04 and 57.3% H2O, or 29.6 lbs. boric acid and 45.1 lbs. sulfate per 100 lbs. of water. Water is removed by evaporation during the process of cooling the solution to about F., and boric acid is removed by crystallization at this lowered temperature. Since more water is evaporated than is necessary to balance thesystemwith respect to water, some further water must be added to the system. This can be used to regulate the amount of boric acid crystallization, reducing the crystallization as necessary by diluting the solution in the cooling tank, and adding the remainder of the water to the solution after extraction ofthe boric acid crystals in centrifuge 16. By adjusting the added Water in this way so that 17.7 lbs. of boric acid are crystallized out and a net loss of 9.6 lbs. of water is effected per 100 lbs. of solution originally entering the cooling tank, the resulting solution has the same composition given above for the original mother liquor. It can therefore be returned directly to storage tank I4, and used for another cycle of the system.

This detailed example is based upon the use of tincal ore, the soluble portion of which is largely borax. Other sodium borates than boraX can also be treated by our process, and the principal modications which are then necessary in the procedure are concerned with the Water balance of the system. For example, if kernite is used as raw material, only four mols of Water are introduced into the solution With each mol of sodium tetraborate. Therefore considerably more Water can be added to the secondthickener and the Water removed by evaporation will still be sucient to maintain the water balance. It may under certain circumstances be desirable to partially dehydrate either tincal ore or kernite before introducing it as raw material in the present process. For example the expense of shipping ore long distances can be reduced by eliminating a part of the Water of crystallization; or an intermediate Waste product from another process, such as middlings from the production of calcined kernite may be employed as raw material.

We claim:

In a cyclic process for producing boric acid from sodium berate containing ore, Which process includes the steps of mixing the ore With an aqueous mother liquor to dissolve the borate, separating the resulting mixture ofborate solution and insoluble material into a primary solution part which is relatively solid-free and a solid-containing part, acidulating the primary solution to form horic acid and sodium sulfate, precipitating sodium sulfate from the treated primary solution at a relatively elevated temperature, removing the precipitate, cooling the remaining solution and thus crystallizing boric acid from the remaining solution at a relatively lower temperature, removing the boric acid crystals and returning the remaining solution as mother liquor for repetition of the cycle; the improvement which comprises diluting the said solid-containing part, separating the diluted solid-containing part into a relatively dilute secondary solution which is relatively solidfree and a second solid-containing part, acidulating the sodium berate of the secondary solution to produce boric acid and sodium sulfate, combining the relatively dilute secondary solution, before removing any solutes therefrom, with the primary solution after the said step of removing precipitated sodium sulfate from the primary solution and before completion of the said step of crystallizing boric acid from the primary solution, and cooling the combined solutions for precipitation of boric acid by evaporation of Water therefrom, precipitation of sodium sulfateY during that evaporative cooling being prevented by suicient dilution of the primary solution, that dilution of the primary solution being produced primarily by its combination With the relatively dilute secondary solution, and the overall balance of the system being maintained substantially constant With respect to water, sodium sulfate and boric acid.

PATRICK JOSEPH OBRIEN. RONALD VALDA CHETTLE.

REFERENCES CITED The following references are of record in the ille of this patent:

UNITED STATES PATENTS Number Name Date 1,216,187 Trump Feb. 13, 1917 1,424,447 Burnham Aug. 1, 1922 1,516,550 Smith Nov. 25, 1924 1,790,436 Mumford Jan. 27, 1931 1,944,548 Ebner Jan. 23, 1934 1,944,598 Franke Jan. 23, 1934 1,950,106 Franke Mar. 6, 1934 2,045,301 Langer June 23, 1936 2,104,009 Burke Jan. 4, 1938 FOREIGN PATENTS Number Country Date 192,032 Great Britain Nov. 26, 1923 

